抗生素在环境中的迁移转化及生物效应研究进展

抗生素被长期大量地使用于人和动物的疾病治疗,同时作为饲料添加剂长期使用于畜牧业及水产养殖业。然而,大部分抗生素不能完全被机体吸收,大量的抗生素以原形或代谢物形式经由病人和禽畜粪尿排入环境,经不同途径进入土壤和水体,从而造成环境污染。多项研究显示在城镇废水和地表水中检测到了抗生素的存在,但关于抗生素在环境中的迁移转化及生物效应等研究资料很少。环境中的抗生素会对微生物、水生生物、土壤生物和植物等产生危害,并产生大量耐药菌,影响禽畜等的正常生长,进而对人类健康及整个生态系统构成威胁。为评估抗生素在环境中潜在的危害,本文就抗生素在环境中的迁移转化以及生物效应等多方面进行综述,并提出了今后研究的方向。     

Dairy manure as a potential source of crop nutrients and environmental contaminants

Although animal manure is applied to agricultural fields for its nutrient value, it may also contain potential contaminants. To determine the variability in such contaminants as well as in valuable nutrients, nine uncomposted manure samples from Idaho dairies collected during 2.5 years were analyzed for macro- and micro-nutrients, hormones, phytoestrogens, antibiotics, veterinary drugs, antibiotic resistance genes, and genetic elements involved in the spread of antibiotic resistance. Total N ranged from 6.8 to 30.7 (C:N of 10 to 21), P from 2.4 to 9.0, and K from 10.2 to 47.7 g/kg manure. Zn (103 – 348 mg/kg) was more abundant than Cu (56 – 127 mg/kg) in all samples. Phytoestrogens were the most prevalent contaminants detected, with concentrations fluctuating over time, reflecting animal diets. This is the first study to document the presence of flunixin, a non-steroidal anti-inflammatory drug, in solid stacked manure from regular dairy operations. Monensin was the most frequently detected antibiotic. Progesterones and sulfonamides were regularly detected. We also investigated the relative abundance of several types of plasmids involved in the spread of antibiotic resistance in clinical settings. Plasmids belonging to the IncI, IncP, and IncQ1 incompatibility groups were found in almost all manure samples. IncQ1 plasmids, class 1 integrons, and sulfonamide resistance genes were the most widespread and abundant genetic element surveyed, emphasizing their potential role in the spread of antibiotic resistance. The benefits associated with amending agricultural soils with dairy manure must be carefully weighed against the potential negative consequences of any manure contaminants.     

Antibiotic resistance genes in manure-amended paddy soils across eastern China: Occurrence and influencing factors

• Manure fertilization resulted in antibiotic residues and increased metal contents. • The tet and sul genes were significantly enhanced with manure fertilization. • Soil physicochemical properties contributed to 12% of the variations in ARGs. • Soil metals and antibiotics co-select for ARGs. Pig manure, rich in antibiotics and metals, is widely applied in paddy fields as a soil conditioner, triggering the proliferation of antibiotic resistance genes (ARGs) in soil. However, comprehensive studies on the effects of manure fertilization on the abundance of ARGs and their influencing factors are still insufficient. Here, pig manure and manure-amended and inorganic-amended soils were collected from 11 rice-cropping regions in eastern China, and the accumulation of antibiotics, metals, and ARGs was assessed simultaneously. The results showed that manure fertilization led to antibiotic residues and increased the metal content (i.e., Zn, Cu, Ni, and Cr). Tetracycline and sulfonamide resistance genes (tetM, tetO, sul1, and sul2) were also significantly enhanced with manure fertilization. According to variance partitioning analysis, the most important factors that individually influenced ARGs were soil physicochemical properties, accounting for 12% of the variation. Significant correlations between soil nutrients and ARGs indicated that manure application enhanced the growth of resistant microorganisms by supplying more nutrients. Metals and antibiotics contributed 9% and 5% to the variations in ARGs, respectively. Their co-occurrence also increased the enrichment of ARGs, as their interactions accounted for 2% of the variation in ARGs. Interestingly, Cu was significantly related to most ARGs in the soil (r = 0.26–0.52, p<0.05). Sulfapyridine was significantly related to sul2, and tetracycline resistance genes were positively related to doxycycline. This study highlighted the risks of antibiotic and ARG accumulation with manure fertilization and shed light on the essential influencing factors of ARGs in paddy soils.     

HPLC-三重四级杆质谱法测定医疗废水中抗生素残留

采用固相萃取/高效液相色谱-三重四级杆质谱法同时测定医疗废水中的20种超痕量抗生素残留,通过优化试验条件,使方法在100μg/L～100μg/L范围内线性良好,方法检出限为024ng/L～122ng/L。空白水样和实际水样3个质量浓度水平的加标回收率分别为80.2%～108%和75.8%～114%,6次测定结果的RSD分别为2.4%～8.4%和1.7%～8.1%。将该方法用于测定重庆市2家三甲医院医疗废水中的超痕量抗生素残留,结果有11种抗生素检出,其余均为未检出。     

Degradation and removal methods of antibiotics from aqueous matrices--a review

Over the past few years, antibiotics have been considered emerging pollutants due to their continuous input and persistence in the aquatic ecosystem even at low concentrations. They have been detected worldwide in environmental matrices, indicating their ineffective removal from water and wastewater using conventional treatment methods. To prevent this contamination, several processes to degrade/remove antibiotics have been studied. This review addresses the current state of knowledge concerning the input sources, occurrence and mainly the degradation and removal processes applied to a specific class of micropollutants, the antibiotics. In this paper, different remediation techniques were evaluated and compared, such as conventional techniques (biological processes, filtration, coagulation, flocculation and sedimentation), advanced oxidation processes (AOPs), adsorption, membrane processes and combined methods. In this study, it was found that ozonation, Fenton/photo-Fenton and semiconductor photocatalysis were the most tested methodologies. Combined processes seem to be the best solution for the treatment of effluents containing antibiotics, especially those using renewable energy and by-products materials.     

Sulfamethoxazole sorption by sediment fractions in comparison to pyrene and bisphenol A

The environmental behavior of antibiotics has attracted great research attention. However, their sorption mechanisms in soils/sediments are still unknown. Comparison of the sorption properties between the widely-studied hydrophobic organic contaminants (HOCs) and antibiotics may provide valuable insight to antibiotic sorption mechanisms. Thus, in this study batch experiments for pyrene (PYR), bisphenol A (BPA), and sulfamethoxazole (SMX) sorption were conducted on a sediment sample and its separated fractions. Our results showed the high sorption of PYR on black carbon and organic matter. Although high sorption of SMX was observed for both separated organic fractions (humic acids) and inorganic mineral particles, the original sediment particles showed relatively low sorption. Competitive sorption between SMX and dissolved humic acid on mineral particles was observed in this study. This competitive interaction is a unique process for antibiotic sorption in soils/sediments compared with apolar HOCs and may be one of the important factors controlling the antibiotic sorption.     

Occurrence and source analysis of typical veterinary antibiotics in manure, soil, vegetables and groundwater from organic vegetable bases, northern China

The residue of antibiotics is becoming an intractable environmental problem in many organic vegetable bases. However, their residual levels and distribution are still obscure. This work systematically analyzed the occurrence and migration of typical veterinary antibiotics in organic vegetable bases, northern China. The results showed that there was no obvious geographical difference in antibiotic distribution between soil and manure. A simple migration model can be easy and quick to predict the accumulation of antibiotics in soil. Antibiotics were mainly taken up through water transport and passive absorption in vegetables. The distribution of antibiotics in a plant was in the sequence leaf > stem > root, and performed biological accumulation. The residues of antibiotics in all samples in winter were significantly higher than those in summer. Overall, this work can lay the foundation for understanding ecological risk of antibiotics and their potential adverse effects on human health by food chain.     

辽宁省生态清洁小流域抗生素监测及生态风险评估

于2021年10月对辽宁省生态清洁小流域抗生素的赋存浓度、分布特征进行了调查。采用风险商值法对小流域的抗生素生态风险进行评价。结果表明,辽宁省生态清洁小流域中8种抗生素均有不同程度检出,检出总质量浓度范围为0013～0.313 μg/L,平均值为0.072 μg/L;小流域中抗生素质量浓度均低于我国大部分河流和流域。不同类型抗生素空间分布规律差异明显,检测出的抗生素中,质量浓度最高的是罗红霉素（ROX）,检出率最高的是磺胺甲噁唑（SMX）;各监测点位抗生素组分的占比排序为：SMX＞ROX＞替米考星（TIC）＞氟苯尼考（FFC）;抗生素主要来源是畜禽养殖和生活污水。生态风险评价结果显示,ROX、脱水红霉素（ERY-H₂O）、诺氟沙星（NOR）和SMX存在高风险,其余种类呈现中、低风险。生态清洁小流域水体中暴露出的抗生素生态风险不容忽视,亟待进一步探究环境风险并采取有效的防治措施。     

Antibiotic contamination in a typical water-rich city in southeast China: a concern for drinking water resource safety

Abstract

The occurrence and distribution in the aquatic environment of Nanjing of 49 antibiotics from seven therapeutic classes were investigated using an improved analytical method developed for multiclass target analysis. The results showed that these antibiotics are widely present in the water bodies of this city, with a total concentration of up to 1.958?μg L^?1. The most abundant class was tetracyclines, contributing 43.7% to the total antibiotic burden. Lincomycin was detected in all samples, and the detection rate of clindamycin was 90.5%. An exploratory analysis of the data points was performed by unsupervised pattern recognition (hierarchical cluster analysis, HCA) in an attempt to clarify the pollution level in different sampling areas, and robust cluster solutions grouped the data according to their different antibiotic contaminant profiles. The safety of drinking water resources was emphasized, and the rivers, as the main receiving water body for treated and untreated wastewater in this city, were more seriously contaminated than the surrounding lakes and reservoir, not only in concentration but also in detection frequency, in our study as well as in similar research studies. A correlation analysis between the presence of antibiotics and the environmental factors was conducted, and it was found that antibiotic contamination and water quality were closely connected; the better the water quality, the lower the antibiotic contamination. Positive correlations existed between the antibiotics and tested heavy metals, as well as between antibiotics and boron and arsenic. However, whether these correlations resulted from their reaction or a common source was difficult to determine, and the mechanism requires further exploration.     

Multi-function adsorbent-photocatalyst MXene-TiO2 composites for removal of enrofloxacin antibiotic from water

MXenes, a new family of two-dimensional transition metal carbides or nitrides, have attracted tremendous attention for various applications due to their unique properties such as good electrical conductivity, hydrophilicity, and ion intercalability. In this work, Ti₃C₂ MXene, or MX, is converted to MX-TiO₂ composites using a simple and rapid microwave hydrothermal treatment in HCl/NaCl mixture solution that induces formation of fine TiO₂ particles on the MX parent structure and imparts photocatalytic activity to the resulting MX-TiO₂ composites. The composites were used for enrofloxacin (ENR), a frequently found contaminating antibiotic, removal from water. The relative amount of the MX and TiO₂ can be controlled by controlling the hydrothermal temperature resulting in composites with tunable adsorption/photocatalytic properties. NaCl addition was found to play important role as composites synthesized without NaCl could not adsorb enrofloxacin well. Adding NaCl into the hydrothermal treatment causes sodium ions to be simultaneously intercalated into the composite structure, improving ENR adsorption greatly from 1 to 6 mg ENR/g composite. It also slows down the MX to TiO₂ conversion leading to a smaller and more uniform distribution of TiO₂ particles on the structure. MX-TiO₂/NaCl composites, which have sodium intercalated in their structures, showed both higher ENR adsorption and photocatalytic activity than composites without NaCl despite the latter having higher TiO₂ content. Adsorbed ENR on the composites can be efficiently degraded by free radicals generated from the photoexcited TiO₂ particles, leading to high photocatalytic degradation efficiency. This demonstrates the synergetic effect between adsorption and photocatalytic degradation of the synthesized compounds.